CN102159313A - Method for producing catalyst for reforming tar-containing gas, method for reforming tar and method for regenerating catalyst for reforming tar-containing gas - Google Patents

Method for producing catalyst for reforming tar-containing gas, method for reforming tar and method for regenerating catalyst for reforming tar-containing gas Download PDF

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CN102159313A
CN102159313A CN2009801369557A CN200980136955A CN102159313A CN 102159313 A CN102159313 A CN 102159313A CN 2009801369557 A CN2009801369557 A CN 2009801369557A CN 200980136955 A CN200980136955 A CN 200980136955A CN 102159313 A CN102159313 A CN 102159313A
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catalyst
reforming
gas
tar
tar gas
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铃木公仁
藤本健一郎
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Nippon Steel Corp
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Nippon Steel Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/18—Modifying the properties of the distillation gases in the oven
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1252—Cyclic or aromatic hydrocarbons
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

Provided is a method for producing a catalyst for reforming a highly active tar-containing gas to be used in subjecting a crude gas, which is generated in the course of the heat decomposition of a carbonaceous material, to a treatment for chemical energy conversion whereby the crude gas is converted in the presence of the catalyst into light hydrocarbons to thereby give a fuel composition comprising methane, hydrogen and so on as the major components with the use of the sensible heat of the crude gas and the high chemical reactivity of hot tar that is contained in the crude gas or associated therewith.

Description

Contain manufacture method, the coke tar reforming method of the catalyst for reforming of tar gas and contain the renovation process of the catalyst for reforming of tar gas
Technical field
The high temperature that produces when the present invention relates to the carbon raw material thermal decomposition contains that tar gas is reformed and the manufacture method of the catalyst for reforming that transforms to the gas that with hydrogen, carbon monoxide, methane is the center, the renovation process when having used the tar gasification process (reforming method) of this catalyst and having contained the catalyst for reforming deterioration of tar gas.
The application based on September 24th, 2008 spy in Japanese publication be willing to 2008-244852 number and advocate its content to be incorporated herein priority.
Background technology
Steel industry is about one one-tenth the high energy-consuming industry that accounts for Japanese total power consumption amount, but in the continuous iron-smelting process of blast furnace process about four one-tenth be the used heat that does not utilize.Wherein, though, the sensible heat of the not purification of CO G (coke oven gas, hereinafter referred to as " thick COG ") of the high temperature that is produced by coke oven is arranged as reclaim the thermal source be not utilized easily in the past.Recovery technology as the sensible heat of this thick COG, previous patent document 1 and 2 has proposed to be recovered as with indirect thermal the method for main body, they disclose following method: inner or between tedge portion and discharge portion, heat-transfer pipe is set at the coke oven tedge, and thermal medium is circulated in this heat-transfer pipe inner loop reclaim sensible heat.But, in these methods, be accompanied by the tar that produces COG, light oil etc. to the adhering to of heat-transfer pipe outer surface, densified aggravation that carbonization and cohesion caused, through the time reduction of heat transfer efficiency and the problem that heat exchanger effectiveness reduces be inevitable.As the technology that addresses these problems, patent documentation 3 discloses following method: at catalyst such as heat-transfer pipe outer surface coating crystallinity aluminosilicate, crystallinity silica, Jie is resolved into low-molecular-weight hydrocarbon by catalyst with attachments such as tar, thereby stably keeps heat transfer efficiency.But this method is not jumped out the category of the indirect thermal recovery technology of thick COG sensible heat yet, and in addition, whether the catabolite of not considering heavy hydrocarbon such as tar fully becomes easily the light hydrocarbon that utilizes as gaseous fuel etc. etc.And then, the catalyst poisoning sulphur compounds such as hydrogen sulfide of also not studying the high concentration that contains among the thick COG become degrading activity that branch causes through the time deterioration influence.
On the other hand, about character according to the difference of temperature and the chemical energy transformation technology of the so-called heat energy that heat energy is changed into chemical energy that changes greatly, the association system of gas turbine combined cycle power plant (GTCC) with other complete set of equipments proposed, for example, with the combination (patent documentation 4) that has utilized high temperature oxygen to carry the oxygen of property solid electrolyte to make, the steam reforming of natural gas that has utilized gas turbine outlet exhaust sensible heat and hydrogen manufacturing and fuel utilization (patent documentation 5) thereof etc. everywhere as seen.Any technology all is to be that medium acts on air, natural gas with solid electrolyte, this class functional material of catalyst, thereby changes into the technology of oxygen, this class chemical energy of hydrogen.
For the reactant gas that at high temperature generates, utilize its sensible heat, the technology that directly imports chemical reaction and change into chemical energy in the presence of catalyst does not have substantially, all is that the sensible heat of high-temperature gas is reclaimed indirectly or is not utilized fully and chilled gas is carried out the situation that various processing are used basically in the past.But, though thick COG has sensible heat, but the content of sulphur compound surpasses 2000ppm, viewpoint from the related catalyst reaction design of the decomposition reaction of heavy hydrocarbons such as tar, think that above-mentioned technology extremely is difficult to realize, as putting down in writing in the patent documentation 6, study up to now, but reforming activity may not can be described as fully.In addition, the energy reforming catalyst usually adopts from the outside reactive metal kind is supported on and supports method manufacturing on the porous ceramic carriers such as silica, aluminium oxide, but this method is difficult to improve the dispersiveness of carrying metal composition, and separated out by sulfur poisoning and carbon, be suitable under the above-mentioned atmosphere that comprises the high concentration sulphur compound, causing easily that carbon separates out based on the catalyst of the decomposition reaction of the tar of condensed polycyclc aromatic so be difficult to make.In addition, behind the performance degradation, carry out air burning for regeneration, cause the sintering (thickization) of carrying metal particle thus easily, also be difficult to realize the reproduction of activity by regenerating in case react.
In addition, manufacture method about the mixture of nickel magnesium oxide compound and aluminium oxide, even merely will carry out moulding after nickel magnesium oxide compound powder and the alumina powder physical mixed, burn till, the existence of each element in the catalyst is heterogeneity also, particularly spike nickel cohesion and surface area does not increase, reforming activity is insufficient, and the carbon amount of separating out is more etc., does not reach the level that can tolerate on practical.
On the other hand, manufacture method as the oxide that contains nickel, magnesium and aluminium, disclose in non-patent literature 1, the patent documentation 8 etc. and utilized precipitating reagent to make the material that burns till behind the sediment (mainly forming hydrotalcite structure) and obtain by the aqueous solution that has dissolved each metal ingredient, but reforming activity is also insufficient and the carbon amount of separating out is more, towards existing problems aspect the practicability.
This wherein, present inventors further investigate, the result distinguishes, the reforming activity height of the catalyst of making by following method, the carbon amount of separating out is fewer, and this has been proposed patent application (Japanese Patent Application 2008-155887 number), said method is: utilize precipitating reagent to form coprecipitate by the aqueous solution that contains nickel composition and magnesium component, dry, calcining back is added alumina powder and water or is added alumina sol, and the mixture that obtains is thus carried out drying and burns till or carry out drying, calcining, moulding and burn till.But thinking also needs further to reduce the carbon amount of separating out for the catalyst of developing the stable activity of long-term demonstration towards practicability.
And then because global warming problem in recent years, as the effective means of cutting down carbon dioxide output, one of carbon raw material is that utilizing of living beings is noticeable, the research that various places all transform in the efficient energy of carrying out relevant living beings.In addition, recently from guaranteeing the viewpoint of energy resource, the research of effective utilization of the relevant coal that carries out of concentrating one's energy is in the past also being considered again to practicability.Wherein, about tar gasification that living beings are generated by destructive distillation, generate thick gas (not processed gas) and utilize the method for its sensible heat, particularly the catalyst with the tar that used catalyst is restructured as the center, with patent documentation 7 grades is that various researchs have been carried out in representative, but same with the decomposition reaction of above-mentioned tar from coal, may not be sufficient from the viewpoint of catalyst activity, catalyst regeneration.
The look-ahead technique document
Patent documentation
Patent documentation 1: Japanese Patent Publication 59-44346 communique
Patent documentation 2: Japanese kokai publication sho 58-76487 communique
Patent documentation 3: Japanese kokai publication hei 8-134456 communique
Patent documentation 4: No. 5516359 communique of United States Patent (USP)
Patent documentation 5: TOHKEMY 2000-54852 communique
Patent documentation 6: TOHKEMY 2003-55671 communique
Patent documentation 7: TOHKEMY 2005-53972 communique
Patent documentation 8: Japanese kokai publication sho 50-4001 communique
Non-patent literature
Non-patent literature 1:F.Basile et al., Stud.Surf.Sci.Catal., Vol.119 (1998)
Summary of the invention
The problem that invention will solve
The sensible heat that the thick gas (not processed gas) that produces when the objective of the invention is to be conceived to the thermal decomposition of carbon raw materials such as coal or living beings is had, a kind of manufacture method and coke tar reforming method that is used for the employed catalyst for reforming of processing of the thick gas that chemical energy transforms is provided simultaneously, described chemical energy is converted into: by utilizing the high chemical reactivity of the high temperature tar that contains in the thick gas and follow, in the presence of catalyst, transform, change into fuel mix thus based on methane, carbon monoxide, hydrogen etc. to the lightweight chemical substance.The tar gas that contains for particularly contain high-concentration hydrogen sulfide for thick COG etc. by the catalyst for reforming of manufacture method manufacturing of the present invention also has high-performance and the higher anti-carbon property separated out.
In addition, the object of the present invention is to provide the renovation process of a kind of tar gasification with catalyst, its by for using this catalyst to carry out gasification reaction deterioration catalyst, import steam or air and form oxidizing atmosphere, remove thus on the catalyst separate out carbon, absorption sulphur, recover catalyst activity, thereby can stably move.
Be used to solve the means of problem
Present inventors are conceived to constitute the element of catalyst, form and carry out Catalyst Design, its manufacture method is furtherd investigate, the result, as the tar that contains in thick gas when the thermal decomposition of carbon raw material of the present invention and follow to methane, carbon monoxide, hydrogen etc. are the catalyst that the lightweight chemical substance of main body transforms, be conceived to the solid phase crystallization, this solid phase crystallization with in the past to support method different, the spike metal has following various feature: owing to can finely be separated out and can be reacted at a high speed, the reactive metal of being separated out combines securely with matrix (parent phase), so easy-sintering (thickization) not, can suppress active reduces, and can be by burning till the spike metal solid solution in matrix once more of will be separated out, and can carry out regeneration that can suppress sintering etc.Particularly, found following manufacture method: in advance will be as the nickel element and the aluminium oxide that becomes matrix of spike by utilizing, magnesia etc. carry out the chemical combination materialization, adopt reduction before the reaction to handle to make the nickel metal from oxide matrix with bunch shape in the fine this point of separating out of oxide surface, even thereby under the atmosphere of the high concentration of the sulphur composition that can cause sulfur poisoning, containing heavy hydrocarbons such as tar etc. in a large number causes under the harsh situation of the composition that carbon is separated out easily, because even the surface area of reactive metal is big and suffer sulfur poisoning also can separate out reactive metal again, therefore can be with heavy hydrocarbon to methane, carbon monoxide, lightweight chemical substances such as hydrogen transform.
And then find, by carrying out down and the mixing of the alumina adhesive that is used for above-mentioned nickel and magnesian compound moulding are added moistening, thereby the admixture height of nickel and magnesian compound and aluminium oxide homogenizes, carry out drying, the moulding after pulverizing, burn till or carry out drying, calcining, pulverizing, moulding and burn till and the molded catalyst bodies made demonstrates high reforming activity, and can reduce the carbon amount of separating out thereafter.
Below, feature of the present invention is shown.
(1) a kind of manufacture method that contains the catalyst for reforming of tar gas is characterized in that, adds precipitating reagent in the mixed solution of nickel compound and magnesium compound, makes nickel and magnesium co-precipitation and generates sediment; In this sediment, add alumina powder and water or add alumina sol and mix and generate mixture; This mixture is carried out drying at least and burns till, thereby make catalyst.
(2) according to (1) described manufacture method that contains the catalyst for reforming of tar gas, it is characterized in that, said mixture is carried out drying and burns till or carry out drying, calcining, pulverizing, moulding and burn till, thereby make catalyst.
(3) a kind of manufacture method that contains the catalyst for reforming of tar gas is characterized in that, adds precipitating reagent in the mixed solution of nickel compound and magnesium compound, makes nickel and magnesium co-precipitation and generates sediment; In this sediment, add alumina powder and water or add alumina sol and mix and generate mixture; With this mixture after the dry and calcining, further mixed oxidization aluminium powder and water or mixed aluminium oxides colloidal sol and generate the 2nd mixture; The 2nd mixture is carried out drying at least and burns till, thereby make catalyst.
(4) according to (3) described manufacture method that contains the catalyst for reforming of tar gas, it is characterized in that, above-mentioned the 2nd mixture is carried out drying and burns till or carry out drying, calcining, pulverizing, moulding and burn till, thereby make catalyst.
(5) according to each described manufacture method that contains the catalyst for reforming of tar gas in (1)～(4), it is characterized in that the catalyst for reforming that contains tar gas of above-mentioned manufacturing is that 1～50 quality %, content of magnesium are that the content of 5～45 quality %, aluminium oxide is that the mode of 20～80 quality % is made according to nickel content.
(6) according to (5) described manufacture method that contains the catalyst for reforming of tar gas, it is characterized in that the catalyst for reforming that contains tar gas of above-mentioned manufacturing is that 1～35 quality %, content of magnesium are that the content of 10～25 quality %, aluminium oxide is that the mode of 20～80 quality % is made according to nickel content.
(7) a kind of reforming method that contains tar gas, it has used the catalyst for reforming that contains tar gas by each described manufacture method manufacturing in above-mentioned (1)～(6).
(8) according to (7) described reforming method that contains tar gas, it is characterized in that, above-mentioned contain the tar gas catalyst for reforming in the presence of or in the presence of the above-mentioned catalyst after the reduction, make it to contact with the hydrogen, carbon dioxide and the steam that contain in the tar gas that with the carbon raw material thermal decomposition time, produce, thereby with above-mentioned coke tar reforming and the gasification that contains in the tar gas.
(9) according to (8) described reforming method that contains tar gas, it is characterized in that, the tar gas that contains that produces when making above-mentioned thermal decomposition contacts any gas at least hydrogen, carbon dioxide, the steam from the outside, thereby contains with above-mentioned that tar gas is reformed and gasification.
According to each described reforming method that contains tar gas in (7)～(9), it is characterized in that (10) the above-mentioned tar gas that contains is the tar gas that contains that contains the above hydrogen sulfide of 20ppm.
(11) according to each described reforming method that contains tar gas in (7)～(10), it is characterized in that, in above-mentioned reformed gas, further add oxygen-containing gas and it is contacted with the above-mentioned tar gas that contains, thereby make above-mentioned part hydrogen or the hydrocarbon burning that contains in the tar gas.
(12) according to each described reforming method that contains tar gas in (7)～(11), it is characterized in that the above-mentioned tar gas that contains is the carbonizing gas that produces when coal is carried out destructive distillation.
According to each described reforming method that contains tar gas in (7)～(11), it is characterized in that (13) the above-mentioned tar gas that contains is the coke oven gas of discharging from coke oven.
(14) according to each described reforming method that contains tar gas in (7)～(11), it is characterized in that, above-mentioned contain tar gas be to wooden be living beings, castoff be in the living beings any one carries out destructive distillation at least the time carbonizing gas that produces.
(15) according to each described reforming method that contains tar gas in (7)～(14), it is characterized in that, the above-mentioned tar gas that contains is contacted with the above-mentioned tar gas catalyst for reforming that contains down at 600～1000 ℃.
(16) a kind of renovation process that contains the catalyst for reforming of tar gas, it is characterized in that, each described enforcement that contains the reforming method of tar gas in by (7)～(15), above-mentioned catalyst owing to carbon is separated out, in the sulfur poisoning any one has taken place under the situation of performance degradation at least, make steam or airborne any one contacts with above-mentioned catalyst at least, thereby with above-mentioned catalyst regeneration.
The invention effect
According to the present invention, can make a kind of catalyst for reforming with high activity and higher anti-carbon property separated out, the tar that contains in its thick gas that produces in the time of can be with the thermal decomposition of carbon raw material and follow transforms to the lightweight chemical substance in the presence of catalyst, changes into the fuel mix based on methane, carbon monoxide, hydrogen etc. thus.Particularly can make the catalyst for reforming that tar gas also has high-performance and the higher anti-carbon property separated out that contains that contains high-concentration hydrogen sulfide for biomass gasified gas body or thick COG etc.In addition, according to a mode of the present invention, can utilize the sensible heat that contains tar gas that tar is changed into the lightweight chemical substance.
Description of drawings
Fig. 1 is the part of coke oven gas is discharged in expression from coke oven figure.
Fig. 2 be explanation among the embodiment dry distillation of coal technology and use the figure that contain technology that tar gas reform of catalyst to wherein producing.
Fig. 3 is the wide-angle x-ray diffraction pattern of the part at Ni (200) peak that is equivalent to reacted catalyst among the embodiment 2.
Fig. 4 is the wide-angle x-ray diffraction pattern of the part at Ni (200) peak that is equivalent to reacted catalyst in the comparative example 5.
The specific embodiment
Below, concrete example is shown, the present invention is described in more detail.
For the catalyst for reforming that contains tar gas that adopts manufacture method manufacturing of the present invention, nickel (Ni) exists in heavy hydrocarbon and the gas or brings into play function from carrying out the main active of reforming reaction between the steam of outside importing, hydrogen, the carbon dioxide as making.Even under the situation of the hydrogen sulfide of the high concentration that in containing tar gas, coexists, since above-mentioned nickel metal on catalyst surface with the fine dispersion of bunch shape, thereby surface area is big, even and under reducing atmosphere in reaction active metal particles poisoned and also separated out new active metal particles from matrix is fine, so think the influence that the activity that also is not vulnerable to cause because of sulfur poisoning reduces.Active metal particles is separated out with fine bunch of shape from this matrix compounds.In addition, can think, also be under the condition of high temperature after the destructive distillation just based on the tar of condensed polycyclc aromatic and be imbued with reactive state, and by having the highly active nickel Metal Contact of high-specific surface area, transform and decompose to light hydrocarbon expeditiously with fine dispersion.In addition, can think, carry out in the composition of chemical combination materialization with nickel element, magnesia is basic anhydride, the function of possessing absorbing carbon dioxide, thereby thereby separating out carbon reaction and form carbon monoxide and carry out the effect that oxidation is removed on performance and the main active element, thus can keep the catalyst surface cleaning, and can keep catalytic performance steadily in the long term.Can think, aluminium oxide keeps the function of the adhesive of compound matrix with playing stably, and by separate the crystalline phase that contains nickel, magnesium finely, make its high degree of dispersion etc. in the oxide solid phase, to precipitate into the nickel shot of spike on surface from each crystalline phase less and be in the function of the dispersity of height thereby performance makes.
Here so-called " carbon raw material " is to carry out thermal decomposition and the raw material that generates the carbon containing of tar, is meant the raw material that comprises the wide region of carbon in the formation elements such as container package class of coal and living beings, plastics.Wherein, so-called " living beings " are meant, the residual material in forest land, thinnings, the trees, the timber that do not utilize processes residual material, build waste wood or with they be the secondary products such as wooden bits, particle etc. of raw material wooden be living beings; The papermaking such as waste paper that can not utilize again as recycled writing paper are living beings; With short bamboo, Chinese silvergrass be representative in the park, the draft such as weeds class that extract of river, road are living beings; Castoffs such as garbage class are living beings; Agriculture residues such as rice straw, wheat straw, rice husk; The resource crop of greases such as saccharic resources such as sugarcane, corn and other starches resource and vegetable seed etc.; Mud; Cattle waste etc.
In addition, so-called " tar " that produces during with the carbon raw material thermal decomposition, though proterties, is meant that what comprise 5 above carbon is the organic compound of liquid at normal temperatures according to the difference of the raw material that is thermal decomposited and difference, is the mixture that comprises chain type hydrocarbon, ring type hydrocarbon etc.Particularly, if the thermal decomposition of coal, then for example condensed polycyclc aromatics such as naphthalene, phenanthrene, pyrene, anthracene etc. are main component, if wooden be the thermal decomposition of discarded object, be main component for example then with benzene, toluene, naphthalene, indenes, anthracene, phenol etc., if the thermal decomposition of castoff, then for example except above-mentioned, comprise that also indoles, pyrroles etc. contain the heterocyclic compound of xenogenesis elements such as nitrogen element in hexatomic ring or five-membered ring, but be not defined in these especially.Thermal decomposition tar exists with gaseous state under the condition of high temperature after the thermal decomposition.
In addition, make the tar catalytic cracking and the reaction of the coke tar reforming that gasifies is to be the reaction that the tar of main body transforms to lightweight chemical substances such as methane, carbon monoxide, hydrogen by heavy hydrocarbon.Response path is complicated and may not be clear, but can consider and contain in the tar gas or from the hydrogenation that can cause between the hydrogen of outside importing, steam, the carbon dioxide etc., steam reforming reaction, dry type reforming reaction etc.This a series of reaction is owing to be the endothermic reaction, so in the time of in being applied to physical device, the gas that enters into the sensible heat with high temperature of reactor is reformed in catalyst layer, reduce in the exit temperature, but when more expeditiously heavy hydrocarbon compositions such as tar being reformed, by as required air or oxygen being imported in the catalyst layer, further carry out reforming reaction when making the part hydrocarbon become the combustion heat that divided combustion produces to remain on the temperature of catalyst layer to a certain degree thereby can utilize.
Reforming catalyst of the present invention is following to be made: use precipitating reagent and generate sediment in the mixed solution of nickel compound and magnesium compound; Under the situation of this sediment not carried out drying and burning till, in this sediment, add alumina powder and water or add alumina sol and mix and generate mixture; This mixture is carried out drying at least and burns till, thereby make reforming catalyst of the present invention.Perhaps, reforming catalyst of the present invention is following to be made: add precipitating reagent in the mixed solution of nickel compound and magnesium compound, make nickel and magnesium co-precipitation and generate sediment; Under the situation of this sediment not carried out drying and burning till, in this sediment, add alumina powder and water or add alumina sol and mix and generate mixture; With this mixture after the dry and calcining, further mixed oxidization aluminium powder and water or mixed aluminium oxides colloidal sol and generate the 2nd mixture; The 2nd mixture is carried out drying at least and burns till, thereby make reforming catalyst of the present invention.
In addition, as the method that said mixture or the 2nd mixture are carried out drying and burn till at least, the drying of carrying out is arranged and burn till; Or carry out drying, pulverize and burn till; Or carry out drying, pulverizing, moulding and burn till; Or carry out drying, calcining, pulverizing, moulding and burn till; Or carry out drying, pulverizing, calcining, pulverizing, moulding and the method for burning till etc.
Here, about the drying of said mixture, not special limiting temperature, drying means are so long as general drying means gets final product.Dried mixture burns till after carrying out coarse crushing as required and gets final product (sediment after the drying by fluosolids etc. keeps dry is under the situation of powdery, does not need coarse crushing).
In addition, preferably filtered in advance before the drying of mixture, this can reduce dry needed time and labor, and reduces dry energy needed.And then the sediment after more preferably will filtering washs with pure water etc., because this can reduce impurity level.
In addition, burning till of said mixture can be carried out in air, as long as temperature is 700～1300 ℃ a scope.More preferably 900～1150 ℃.When firing temperature was higher, the sintering of mixture constantly carried out, and intensity rises, and but then, because specific area diminishes, so catalyst activity reduces, therefore, expectation considers that its balance decides firing temperature.Can be directly after burning till use, but also can be undertaken using with the form of article shaped after the moulding by compression moulding etc. as catalyst.In addition, can also increase calcining and molding procedure in drying and between burning till, and then between calcining and molding procedure, before moulding, make the powder shape if desired, then after pulverizing, carry out moulding and get final product.In this case, calcining if in air about 400～800 ℃, moulding employing compression moulding etc. gets final product.
By using the catalyst that adopts this manufacture method to make, even what produce during with the carbon raw material thermal decomposition contains a large amount of hydrogen sulfide and causes the tar gas that contains based on condensed polycyclc aromatic that carbon is separated out easily, also the heavy hydrocarbons of following such as tar can be reformed expeditiously, be changed into lightweight chemical substance based on hydrogen, carbon monoxide, methane.In addition, when the catalyst performance deterioration,, can remove separating out carbon, absorption sulphur and recover catalytic performance on the catalyst, thereby can move steadily in the long term by making steam or airborne any one at high temperature contacts with catalyst at least.
For the catalyst for reforming that contains tar gas that adopts the manufacturing of this manufacture method, it is with behind the coprecipitate that forms nickel and magnesium, physical mixed alumina powder and to carry out the catalyst for reforming that moulding obtains with burning till different merely in the powder that has obtained having carried out burning till, by wet mixed alumina powder and water in the sediment of nickel and magnesium or mixed aluminium oxides colloidal sol, can form the mixture that forms the height homogeneous between the coprecipitate at nickel and magnesia at the moisture that contains alumina composition.Therefore can think, by this mixture being carried out drying and burning till or carry out drying, calcining, pulverizing, moulding and burn till, can form the compound of nickel and magnesium and the sintered body that aluminium oxide distributes in heterogeneity, the further miniaturization of nickel magnesium oxide crystalline phase, from the fine to heavens dispersion of its Ni grain of separating out, so can obtain high activity and the less article shaped of the carbon amount of separating out.
Actual evaluation reacted catalyst measure the size of the Ni grain of Ni (200) peak obtain obtaining by the wide-angle x-ray diffraction, result's Ni grain as can be known separates out with the very little state of average grain diameter.
More specifically, at first when making the mixed solution of nickel compound and magnesium compound, preferably use each high metallic compound of solubility in water, for example not only preferably use inorganic salts such as nitrate, carbonate, sulfate, chloride, organic salts such as also preferred use acetate.Particularly preferably be: be considered to after burning till, be difficult for residual nitrate or carbonate or the acetate that causes the impurity of catalyst poisoning.In addition, the precipitating reagent that uses when forming sediment for the solution by them is so long as the precipitating reagent that neutrality～alkalescence that the pH that makes above-mentioned solution mainly precipitates with the form of hydroxide to nickel, magnesium changes then can use any precipitating reagent.Wherein, for example preferably use wet chemical or aqueous sodium carbonate, ammonia spirit or urea liquid etc.
And then, in the reforming catalyst of the present invention, be preferably 1～50 quality % as the nickel content of main active.When nickel content is lower than 1 quality %, owing to can't give full play to the reformation performance of nickel, so not preferred.When nickel content surpasses 50 quality % because it is few to form the content of magnesium, aluminium of matrix, therefore high and easy thickization of the nickel concentration of metal of on catalyst, separating out, might this reaction condition issue natural disposition can through the time deterioration.
In addition, content of magnesium is preferably 5～45 quality %.When content of magnesium is lower than 5 quality %, has the character that is difficult to effectively to utilize the basic anhydride that magnesia has and the carbon that suppresses hydrocarbon separates out, is difficult to keep steadily in the long term the tendency of catalyst performance, so be preferably more than the 5 quality %.When content of magnesium surpasses 45 quality %, owing to other nickel, the content of aluminium tail off, so might can't give full play to the reforming activity of catalyst.
And then the content of aluminium oxide is preferably 20～80 quality %.When the content of aluminium oxide was lower than 20 quality %, owing to the pottery that forms based on the nickel magnesium oxide, intensity significantly reduced when moulding, so not preferred.When the content of aluminium oxide surpasses 80 quality %, because as the nickel of main active, the magnesian ratio step-down that inhibition carbon is separated out, so might can't give full play to the reforming activity of catalyst.
In addition, reforming catalyst of the present invention is that 1～35 quality %, content of magnesium are that 10～25 quality %, alumina content are that the mode of 20～80 quality % is made according to nickel content further preferably.In addition, so-called here aluminium oxide is that state with alumina powder or alumina sol joins the aluminium oxide in the oxide of nickel and magnesium.Add with powder fashionable, preferred thin as far as possible particle diameter, for example preferred average grain diameter is below 100 microns, adds entry etc. during mixing and uses with pulp-like.In addition, add fashionablely with alumina sol, using the particle of aluminium oxide is preferred with the alumina sol of on average counting below 100 nanometers.In addition, for the content with each metal kind is adjusted in the above-mentioned scope, preferred each initiation material of on the basis of calculating, preparing in advance.In addition, form, then modulate according to the cooperation of this moment thereafter and get final product in case catalyst becomes target component.
In addition, except above-mentioned element, can also contain the unavoidable impurities of in catalyst manufacturing process etc., sneaking into or other compositions that can not change catalyst performance, but preferably not sneak into impurity as much as possible.
In addition, the Determination on content method that constitutes each metal kind of above-mentioned reforming catalyst can adopt the method that is called as sweep type high-frequency induction coupled plasma method (ICP).Particularly, after the sample pulverizing, add alkalescence fusing agent (for example sodium carbonate, Boratex etc.), in platinum crucible, carry out heat fused, under heating, all be dissolved in the hydrochloric acid solution after the cooling.With this injection of solution in the icp analysis device time, because sample solution atomization, thermal excitation under the high-temperature plasma state in device, when getting back to ground state, it produces the luminescent spectrum of the intrinsic wavelength of element, so, can carry out qualitative and quantitative to the element kind, the amount that are contained by its emission wavelength and intensity.
Here, catalyst for reforming by the present invention's manufacturing, it can be any form in powder or the formed body, under the situation that is formed body, can be form arbitrarily such as spherical, tubular, ring-type, colyliform, form granular etc. and that form to the honeycomb substrates coated catalysts composition of metal or pottery.In addition, under the situation about in fluid bed, using, use by the be shaped catalyst that obtains etc. such as spray-drying preferable.In addition, under the situation about in fixed bed or moving bed, using,, preferably adopt granulation, extrusion molding, compression moulding, the moulding of system ingot etc., but be not particularly limited in this as forming method.
The reforming method that contains tar gas according to having used the catalyst for reforming that obtains by manufacture method of the present invention can obtain foregoing action effect.Contain in the reforming method of tar gas at this, in the presence of above-mentioned catalyst or after with catalyst reduction, the tar gas that contains that the hydrogen, carbon dioxide or the steam that exist in the gas or import from the outside are produced with the carbon raw material thermal decomposition time contact, thereby the coke tar reforming that will contain in the tar gas also gasifies.Catalyst for reforming preferably reduces, but owing in reaction, reducing, so can not reduce yet.Therefore, in the presence of above-mentioned catalyst or after with catalyst reduction, make steam and the air that imports from the outside or add the tar gas that contains that the mist of aerobic produces with the carbon raw material thermal decomposition time contact, thereby the coke tar reforming that will contain in the tar gas also gasifies.
Here, condition during as reducing catalyst, for the nickel particles as reactive metal is separated out with fine bunch of shape from catalyst of the present invention, as long as be set at than higher temperature and for reducing atmosphere, then be not particularly limited, for example, can be under any one the gas atmosphere at least in containing hydrogen, carbon monoxide, methane or in these reducibility gas, mixed under the gas atmosphere of steam or in these gases, mixed under the atmosphere of inactive gas such as nitrogen.In addition, the reduction temperature preference is as being 600 ℃～1000 ℃, and the recovery time also depends on the catalytic amount of being filled, and for example is preferably 30 minutes～4 hours, so long as whole catalyst of being filled reduce the needed time and get final product, be not subjected to the restriction of this condition especially.
As hydrogen-catalyst reactor, preferably use fixed bed form, fluid bed form, moving bed form etc., as the inlet temperature of this catalyst layer, be preferably 600～1000 ℃.When the inlet temperature of catalyst layer is lower than 600 ℃, owing to can't bring into play the catalytic activity of tar when reforming basically based on the light hydrocarbon of hydrogen, carbon monoxide, methane, so not preferred.On the other hand, when the inlet temperature of catalyst layer surpasses 1000 ℃, owing to reformers such as needing heat resistant structureization becomes expensive, so be disadvantageous economically.In addition, the inlet temperature of catalyst layer is more preferably 650～1000 ℃.In addition, be under the situation of coal at carbon raw material, can under than higher temperature, react, for wooden be that living beings, papermaking are that living beings or castoff are under the situation of living beings etc., can under lower temperature, react.
In addition,,, use coke oven usually, under with the situation of living beings, can use external-heating rotary kiln or mobile pool furnace, fluid bed furnace etc., but be not particularly limited in these as raw material being under the situation of raw material with the coal as the production method that contains tar gas.
Here, for with carbon raw material thermal decomposition or partial oxidation and generate contain tar gas, contain tar gas even the such concentration of hydrogen sulfide of the coke oven gas of the high temperature of discharging from coke oven is very high, also can be by the present invention with coke tar reforming in the gas and gasification.Here so-called thermal decomposition or partial oxidation particularly, are meant destructive distillation or for carbon raw material gasification and only make a part of oxidation manufacturing contain tar gas.In the present coke oven, in stove, heat with destructive distillation behind the filling feed coal and make coke, but as shown in Figure 1, the coke oven gas of generation going along with is collected in the dry main (dry main) 4 as discharge behind the part spraying ammoniacal liquor 2 (ammonia water) and cooling that are called as tedge 1 of furnace roof portion.Yet, although gas componant maintains the sensible heat about 800 ℃ in the tedge 1 of coke oven 3, be chilled to below 100 ℃ behind the spraying ammoniacal liquor 2, can not effectively utilize its sensible heat.Therefore, if can effectively utilize this gas sensible heat and heavy hydrocarbon compositions such as tar are changed into propellant compositions such as light hydrocarbon such as hydrogen, carbon monoxide, methane, then not only being related to energy amplifies, and the reducibility gas volume that wherein generates significantly amplifies, if for example can realize being applied to the technology that iron ore is made reduced iron, then might cut down significantly in the past by coke and come the carbon dioxide output that produces in the blast furnace technology of reducing iron ore.According to the present invention, the coke oven gas of possessing sensible heat that produces in the coke oven is contacted with the catalyst for reforming that adopts manufacture method of the present invention to make, effectively utilize gas sensible heat and reform, can change into the propellant composition of light hydrocarbons such as hydrogen, carbon monoxide, methane etc.
In addition, even catalyst for reforming of the present invention also stably carries out reforming reaction under hydrogen sulfide atmosphere, but the concentration of hydrogen sulfide in the gas is low more, then can not poison more, so preferred.Be preferably the following concentration of 4000ppm especially.And then the more preferably following concentration of 3000ppm.
On the other hand, for the coke tar reforming catalyst that is built in the hydrogen-catalyst reactor, from tar when transforming based on the lightweight chemical substance of hydrogen, carbon monoxide, methane, contained sulphur composition is adsorbed onto on the catalyst in carbon of separating out on catalyst surface or the thermal decomposition gas that obtained by above-mentioned pyrolosis operation, causes the catalyst performance deterioration thus.Therefore, method as with the catalyst regeneration of deterioration imports steam in hydrogen-catalyst reactor, utilize the reaction of steam and carbon to remove the carbon of catalyst surface, perhaps utilize the reaction of steam and sulphur to remove the sulphur that adsorbs on the catalyst, thus can be with catalyst regeneration.In addition, by being replaced to air, part or all of steam import, thereby the carbon of catalyst surface is removed in the combustion reaction that utilizes airborne oxygen and carbon, perhaps utilizes the reaction of oxygen and sulphur to remove the sulphur that adsorbs on the catalyst, thus also can be with catalyst regeneration.
Embodiment
Below, the present invention is described in more detail by embodiment, but the present invention is not limited to these embodiment.
(embodiment 1)
Accurately taking by weighing nickel nitrate and magnesium nitrate makes the mol ratio of each metallic element reach 1: 9, heating modulated mixed aqueous solution at 60 ℃, to the wet chemical that wherein is heated to 60 ℃, make the form co-precipitation of nickel and magnesium with hydroxide, stir fully with agitator.Then, the state that remains on 60 ℃ continues the stirring stipulated time down and carries out slaking, carries out suction filtration then, washs fully with 80 ℃ pure water.Then, the mode of counting 50 quality % with aluminium oxide in resulting sediment adds alumina sol, transfers in the eggplant type flask after fully mixing with the blender that paddle is installed, and is installed on the rotary evaporator, aspirate while stirring, make water evaporates thus.The mixture of the nickel, magnesium and the aluminium oxide that adhere on the eggplant type flask wall transferred under 120 ℃, carry out drying in the evaporating dish, after pulverizing with mortar, use the compression molding device, obtain the tablet formed body the tablet shape of powder pressing forming as 3mm φ.With this formed body in air, under 1100 ℃, burn till, thereby prepared at Ni 0.1Mg 0.9The molded catalyst bodies that has mixed 50 quality % aluminium oxide among the O.
Use this catalyst of 60cc, fixedly be located at the central authorities that SUS makes reaction tube, insert thermocouple, these fixed bed reaction pipes are placed in the position of regulation at the catalyst layer middle position with silica wool.
Before the beginning reforming reaction, at first under blanket of nitrogen, reactor is warming up to 800 ℃ after, the hydrogen that circulated 100cc/ minute carries out reduction processing in 30 minutes on one side.Then, as the analog gas of coke oven gas, according to hydrogen: nitrogen=1: 1, H 2Each gas is adjusted and imported to the mode that S is the concentration shown in the table 1, add up to 125cc/ minute, under normal pressure, carrying out reaction evaluating at each temperature shown in the table 1.In addition, produce the simulation substance of tar during as the dry distillation of coal, use in fact also contain in the tar and viscosity is low at normal temperatures liquid be the 1-methyl naphthalene as representative species, import in reaction tube by the flow of precision pump with 0.025g/ minute.In addition, in reaction tube, import pure water with 0.1g/ minute flow, make (H by precision pump 2The O molal quantity)/(the carbon molal quantity of above-mentioned 1-methyl naphthalene)=3.The generation gas of discharging from outlet, is injected in the gas chromatograph (ヒ ュ one レ ッ ト パ ッ カ one De is made HP6890) after removing naphthalene, moisture respectively via room temperature trap (trap), the warm trap of ice, carries out TCD, FID and analyze.The extent of reaction of reforming reaction (resolution ratio of methyl naphthalene) is utilized methane selection rate, CO selection rate, CO 2The carbon eduction rate of piling up on selection rate, the catalyst is judged.They are calculated by following formula by each constituent concentration in the exit gas.
Methane selection rate (%)=(CH 4Volume)/(the C quantity delivered of the methyl naphthalene of being supplied with) * 100
CO selection rate (%)=(volume of CO)/(the C quantity delivered of the methyl naphthalene of being supplied with) * 100
CO 2Selection rate (%)=(CO 2Volume)/(the C quantity delivered of the methyl naphthalene of being supplied with) * 100
Carbon eduction rate (%)=(separating out carbon weight)/(the C quantity delivered of the methyl naphthalene of being supplied with) * 100
In addition, also put down in writing the ratio (hydrogen magnifying power) of outlet hydrogen volume in the lump with respect to the inlet hydrogen volume.
[table 1]
No. 1 2 3 4 5
Reaction temperature (℃) 600 700 800 900 1000
H 2S concentration (ppm) 2000 2000 2000 2000 2000
Methane selection rate (%) 3.7 2.9 1.6 0.3 0.1
CO selection rate (%) 3.2 16.7 55.5 63.1 67.1
CO 2Selection rate (%) 7.2 12.1 23.1 29.2 28.2
Carbon eduction rate (%) 11.5 11.7 9.6 1.3 0.1
Hydrogen magnifying power (-) 1.3 1.5 2.1 2.3 2.4
Resolution ratio (%) 25.6 43.4 89.8 93.9 95.5
The result of the No.1 of table 1～5 has hinted: even at H 2S concentration is that the such high concentration ground of 2000ppm contains H 2Under the atmosphere of S, also carry out as the decomposition reaction of the methyl naphthalene of simulating tar, its anti-sulfur poisoning of catalyst of being made by this manufacture method is strong.In addition as can be known, particularly in rising, resolution ratio (methane selection rate+CO selection rate+CO along with reaction temperature 2Selection rate+carbon eduction rate) under the harsh situation that height, sulfur poisoning height and the carbon property separated out are high, the decomposition reaction of methyl naphthalene is also carried out.In addition, along with H 2The reduction of S concentration, the influence of sulfur poisoning tails off, and resolution ratio further improves.And then can think that owing to the rising along with the resolution ratio of simulating tar, the hydrogen magnifying power also rises, so the hydrogen that combines with the carbon that constitutes methyl naphthalene is along with the decomposition that causes because of catalyst changes into hydrogen molecule.In addition, the carbon eduction rate is lower numerical value, and temperature rises more, and then the carbon eduction rate becomes low more.Distinguished that in addition whole reforming reaction is also carried out under the high-temperature area more than 800 ℃ effectively, temperature rises more, and then resolution ratio rises more.
(embodiment 2)
The catalyst identical with embodiment 1 burnt till under 950 ℃, and use 30cc, all adopt the method identical in addition, under the condition of table 2, estimated catalyst activity with embodiment 1.Its result is as shown in table 2.
[table 2]
No. 6 7 8 9 10 11
Reaction temperature (℃) 600 700 800 900 800 800
H 2S concentration (ppm) 2000 2000 2000 2000 20 200
Methane selection rate (%) 2.6 2.1 2.2 0.1 1.2 1.5
CO selection rate (%) 2.8 7.6 33.0 62.7 55.6 49.7
CO 2Selection rate (%) 9.6 11.3 29.8 28.3 32.9 29.4
Carbon eduction rate (%) 3.3 6.2 9.5 1.5 1.6 6.5
Hydrogen magnifying power (-) 1.1 1.3 1.8 2.0 2.3 2.2
Resolution ratio (%) 18.3 27.2 74.5 92.6 91.3 87.1
According to the result of No.6～9 of table 2, at H 2S concentration is under the high concentration atmosphere of 2000ppm, and the temperature reforming activity of then simulating tar that raises more rises more till 900 ℃, and resolution ratio improves.In addition, the identical and H with reaction temperature 2When the No.8 that S concentration is different, 10,11 result compared, even the tendency that exists the high more resolution ratio of then simulating tar of concentration to reduce more as can be known was but H 2S concentration is 2000ppm, also demonstrates activity up to 74% 800 ℃ of following resolution ratios.
In addition, according to Ni (200) peak that records by the wide-angle x-ray diffraction that utilizes reacted catalyst the Ni grain is estimated according to as described below.At first, material is placed in powdered sample with after on the retainer, the RINT1500 that uses Rigaku to make, producing the CuK alpha ray with the power output of 40kV, 150mA, is that graphite, divergent slit and scatter slit are 1 °, to be subjected to optical slits be that to be subjected to optical slits be that 0.8mm, sampling width are that 0.01deg, sweep speed are to measure under 2deg/ minute the condition for 0.15mm, monochrome at monochromator.Particularly, measure peak width (the half value width of cloth), use following Scherrer formula to calculate by this value in half position highly of summit for measuring near Ni (200) peak that 2 θ are about 52deg, occurs in the curve.
D hkl＝Kλ/βcosθ
Here, D HklBe the size of crystal grain, so, if utilize Ni (200) diffracted ray to estimate, then represent the size of the crystal grain of Ni.K is a constant, but as follows, owing to use the half value width of cloth as β, so be set at 0.9.λ measures the X ray wavelength, in this mensuration is
Figure BDA0000051369370000171
In addition, β is the expansion of the diffracted ray that size produced of crystal grain, and uses the above-mentioned half value width of cloth.θ is the Bragg angle of Ni (200) diffracted ray.
Pass through this method, employed catalyst in this test is pulverized, the Ni grain of being obtained by Ni (200) peak that utilizes wide-angle x-ray diffraction shown in Figure 3 to obtain is calculated and is 13nm, be evaluated as and separated out very fine Ni grain, can think that this is the main cause that embodies high reforming activity and the high anti-carbon property separated out.
(embodiment 3)
Except the mode of quality % shown in table 3,4 according to nickel, magnesium and aluminium oxide in the oxide of nickel and magnesium is prepared, prepared catalyst similarly to Example 1.In addition, as experiment condition, be 800 ℃, H in reaction temperature 2S concentration is to estimate under 2000ppm, the normal pressure and under the condition of the No.3 of embodiment 1.Its result is shown in table 3,4.
[table 3]
No. 12 13 14 15 16 17 18 19
Ni (quality %) 0.5 1 5 10 12 15 17 25
Mg (quality %) 12 11 10 5 3 25 17 11
Aluminium oxide (quality %) 80 80 80 80 80 50 50 50
Methane selection rate (%) 1.1 1.5 2.4 2.2 2.1 2.0 2.3 2.8
CO selection rate (%) 7.1 18.7 32.6 42.3 41.7 48.5 46.8 45.5
CO 2Selection rate (%) 11.5 18.3 32.2 26.1 28.6 25.7 26.5 27.2
Carbon eduction rate (%) 10.4 11.1 11.9 12.2 13.6 14.1 15.0 16.5
Hydrogen magnifying power (-) 1.2 1.4 1.8 1.9 1.9 2.1 2.2 2.2
Resolution ratio (%) 30.1 49.6 79.1 82.8 86.0 90.3 90.6 92.0
[table 4]
No. 20 21 22 23 24
Ni (quality %) 1 5 35 50 55
Mg (quality %) 47 45 22 15 6
Aluminium oxide (quality %) 20 20 20 20 20
Methane selection rate (%) 1.5 2.3 4.0 4.5 5.1
CO selection rate (%) 17.6 32.2 45.6 45.1 46.6
CO 2Selection rate (%) 19.2 32.7 26.2 27.0 21.5
Carbon eduction rate (%) 9.3 9.9 17.0 17.6 21.8
Hydrogen magnifying power (-) 1.4 1.6 2.2 2.3 2.4
Resolution ratio (%) 47.6 77.1 92.8 94.2 95.0
According to the result of table 3, table 4, more little as the Ni quality of main active, then the resolution ratio of methyl naphthalene is low more, and the hydrogen magnifying power is also low more, and under the situation of Ni quality less than the No.12 of 1 quality %, resolution ratio, hydrogen magnifying power are all lower as a result.On the other hand, the Ni quality is big more, and then resolution ratio, hydrogen magnifying power are also high more.But under the situation of Ni quality above the No.24 of 50 quality %, the result is more for the carbon amount of separating out.In addition, when No.13 and No.20 or No.14 and No.21 were compared, even roughly equal Ni quality, according to the difference of aluminium oxide quality, many persons of alumina composition catalyst activity was higher.Can envision this be because, alumina composition is mutually separated nickel magnesium oxide compound imperceptibly, the size decreases of the Ni metallic of when reduction, separating out, it is big that the reaction table area becomes.In addition, the big more then carbon of Mg quality eduction rate is low more, and under the situation of Mg quality less than the No.16 of 5 quality %, carbon is separated out the quantitative change height.
(embodiment 4)
Except reaction temperature is 800 ℃, H 2When being 2000ppm, reaction, S concentration imports H with each condition shown in the table 5 2O, CO 2And O 2In addition, carry out Preparation of Catalyst, evaluation similarly to Example 1.Its result is as shown in table 5.In addition, H here 2O/C, CO 2/ C and O 2C among the/C represents the C quantity delivered of the methyl naphthalene supplied with.
[table 5]
No. 25 26 27 28
H 2O/C(-) 3 3 3 3
CO 2/C(-) 1 2 0 1
O 2/C(-) 0 0 0.5 0.5
Methane selection rate (%) 2.0 2.0 1.8 1.6
CO selection rate (%) 50.1 51.5 45.6 46.2
CO 2Selection rate (%) 26.0 25.4 36.4 37.1
Carbon eduction rate (%) 11.9 12.3 8.7 8.6
Hydrogen magnifying power (-) 2.1 2.2 2.2 2.3
Resolution ratio (%) 90.0 91.2 92.5 93.5
According to the result of table 5, by import H from the outside 2O or CO 2Or O 2, compare with the result of the No.3 of embodiment 1, confirm reforming reaction and carry out.In addition, import O 2The time, because can be by the combustion heat to utilizing H 2The steam reformation of O or utilize CO 2The dry type heat absorption of reforming carry out thermal compensation, so when the actual reactor of imagination, be unusual effective method.In addition, by importing O 2, the carbon eduction rate further reduces.
(embodiment 5)
In the batch furnace that can simulate coke oven, fill the charcoal of packing into that 80kg uses in the coke oven of reality, be warming up to 800 ℃ accordingly with actual coke oven, thus the actual tar that produces actual coke oven gas and followed.The tar that contains in the tar gas of this moment is about 0.04g/L.Capture this gas by suction pump, be used for experiment.Heating up so that reaction temperature reaches 800 ℃ electric furnace internal configurations reaction tube, portion's setting will be at Ni by manufacture method similarly to Example 1 in the central 0.1Mg 0.9The oxide that has mixed 50 quality % aluminium oxide among the O is shaped to the catalyst of ring-type, with 10NL/ minute hydrogen reduction after 2 hours, make the gas inflow catalyst layer that captures from batch furnace, continued 5 hours and the catalyst decomposes activity of actual coke oven gas and the actual tar followed is estimated.The inlet gas flow is about 10NL/ minute, and the catalyst loading is about 1L.In addition, confirmed that by gas chromatography the inlet gas composition is and the roughly the same composition of actual coke oven gas.In addition, confirm the hydrogen sulfide that contains 2400～2500ppm in this gas.Tar-concentration in the gas is estimated by following method.That is, the vacuum trapping bottle of the 1L that is in vacuum state in advance is installed in the cock that can open and close of the entrance and exit portion that is installed on catalyst layer, is captured each gas by opening cock.Then,, the quality of removing the liquid component behind the carrene is fully carried out quantitatively at normal temperatures to washing in the trapping bottle with carrene.And the tar resolution ratio is obtained with respect to the ratio of the quality of tar ingredients in the catalyst layer inlet gas by the quality of tar ingredients in the catalyst layer exit gas that captures by said method.Consequently, the tar resolution ratio is 89% during through 2 hours after reaction beginning, and the hydrogen magnifying power reaches 2.3 in 5 hourly averages.
(embodiment 6)
After proceeding reaction in 8 hours under the condition of the No.3 of embodiment 1, stop the input of raw material, at N as carrier gas 2Be 60cc/ minute, H 2O is scaled with gas and makes the catalyst layer temperature reach 800 ℃ and keep 5 hours under 60cc/ minute the situation, thereby removes carbon, the sulphur of piling up on the catalyst.Then, the input of beginning raw material under the condition identical again with embodiment 1, results verification is to demonstrating the preceding activity more than 9 one-tenth of regeneration.In addition, the hydrogen concentration in the gas after the reformation in this test is also high, confirms that having changed into hydrogen, carbon monoxide, methane is the gas of main component.
(embodiment 7)
Similarly to Example 6, after proceeding reaction in 8 hours under the No.3 of embodiment 1 condition, stop the input of raw material, at N as carrier gas 2Be to make the catalyst layer temperature reach 800 ℃ and keep 2 hours under 60cc/ minute the situation for 60cc/ minute, air, thereby remove carbon, the sulphur of piling up on the catalyst.Then, the input of beginning raw material under the condition identical again with embodiment 1, results verification is to demonstrating the preceding activity more than 9 one-tenth of regeneration.In addition, the hydrogen concentration in the gas after the reformation in this test is also high, confirms that having changed into hydrogen, carbon monoxide, methane is the gas of main component.
(embodiment 8)
After being warming up to 800 ℃ with rotary kiln shown in Figure 27 as gas retort, use weight feed machine 6 to rotary kiln 7, to import coal cinder with 20kg/ hour feed speed, thereby generation contain the carbonizing gas of tar from the loading hopper 5 that is filled with coal cinder (being classified into 5cm below).Be about 10Nm by induction fan 11 with flow modulation to gas flow 3/ hour state under, this is contained tar gas (carbonizing gas) imports to and is filled with that the catalyst identical with embodiment 1 formed and external diameter is that 15mm φ, internal diameter are 5mm φ, highly are maintained at about in 800 ℃ the catalyst tower 8 for the ring-type preformed catalyst of 15mm and temperature, it is contacted with catalyst, continued 8 hours and the catalyst decomposes activity that contains tar gas is estimated.Then, reformed gas is carried out water-cooled with washer 9, after oily bubbler 10 dedustings, the tower that applies a torch (flare stack) 12 burning and exhaustings.In addition, before dropping into, raw material uses hydrogen 5Nm 3/ hour carry out reduction in 30 minutes to handle.The inlet gas flow is about 10Nm 3/ hour, the catalyst loading is about 15L.The tar that contains in the tar gas of this moment is about 60g/Nm 3In addition, confirming inlet gas by gas chromatography consists of and the roughly the same composition of actual coke oven gas.In addition, contained about 6% moisture evaporation becomes steam and is contained in this gas in the coal as raw material.And then, confirm the hydrogen sulfide that contains 2000～2500ppm in this gas.Tar-concentration in the gas is following to be estimated: from the entrance and exit of catalyst layer to the gas pumping stipulated time, after the tar ingredients by the 5-linked formula impact-actuated sampler (impinger) that is filled with carrene in the captured gas, carry out quantitatively estimating thus for the composition of liquid at normal temperatures behind the carrene to removing.And the tar resolution ratio is obtained with respect to the ratio of the quality of tar ingredients in the catalyst layer inlet gas by the quality of tar ingredients in the catalyst layer exit gas that captures by said method.Consequently, the tar resolution ratio is about 82% during through 3 hours after reaction beginning, and the hydrogen magnifying power reaches 2.35 in 8 hourly averages, and the catalyst dry gasification that contains tar gas of having verified the model plant layout is reflected at and carries out.
(embodiment 9)
Use the equipment identical with embodiment 8, to wherein supplying with building waste wood sheet bits (being classified into 5cm below), utilization remained on 800 ℃ rotary kiln 7 and carries out destructive distillation with 10kg/ hour feed speed, thereby the generation living beings contain tar gas (carbonizing gas).With this contain tar gas import to be filled with except form No.18 with embodiment 3 identical the identical preformed catalyst of other and embodiment 8 and temperature be maintained at about 800 ℃ catalyst tower in, it is contacted with catalyst, continued 8 hours and the catalyst decomposes activity that contains tar gas is estimated.In addition, raw material drops into preceding with 5Nm 3/ hour hydrogen carry out reduction in 30 minutes and handle.The inlet gas flow is about 10Nm 3/ hour, the catalyst loading is about 15L.The tar that the living beings of this moment contain in the tar gas is about 10g/Nm 3In addition, by gas chromatography confirm inlet gas form be with coke oven gas approaching with hydrogen, CO, methane, CO 2Composition for main component.In addition, contained about 16% moisture evaporation becomes steam and is contained in this gas in the building waste wood as raw material.And then, confirm the hydrogen sulfide that contains the 25ppm that has an appointment in this gas.In addition, the method by similarly to Example 8 captures from the entrance and exit of catalyst layer and contains tar ingredients the tar gas, and the focusing oil content carries out quantitatively estimating the tar resolution ratio thus.Its result, tar resolution ratio are 94.4% during through 3 hours after reaction beginning, and the hydrogen magnifying power was stably passed with about 6.5 in 8 hours, and the catalyst dry gasification that the living beings of having verified the model plant layout contain tar gas is reflected at stably and carries out.
(embodiment 10)
Use the equipment identical with embodiment 8, with 10kg/ hour feed speed to the dried pieces of wherein supplying with from the castoff of collections such as supermarket (being classified into below the 5cm), utilization remains on 800 ℃ rotary kiln 7 and carries out destructive distillation, contains tar gas (carbonizing gas) thereby produce living beings.With this contain tar gas import to be filled with except form No.18 with embodiment 3 identical the identical preformed catalyst of other and embodiment 8 and temperature be maintained at about 800 ℃ catalyst tower in, it is contacted with catalyst, continued 8 hours and the catalyst decomposes activity that contains tar gas is estimated.In addition, raw material drops into preceding with 5Nm 3/ hour hydrogen carry out reduction in 30 minutes and handle.The inlet gas flow is about 10Nm 3/ hour, the catalyst loading is about 15L.The tar that the living beings of this moment contain in the tar gas is about 23g/Nm 3In addition, by gas chromatography confirm inlet gas form be with coke oven gas approaching with hydrogen, CO, methane, CO 2Composition for main component.In addition, contained about 30% moisture evaporation becomes steam and is contained in this gas in the melange as the dry product of the castoff of raw material and building waste wood.And then, confirm the hydrogen sulfide that contains the 400ppm that has an appointment in this gas.In addition, the method by similarly to Example 8 captures from the entrance and exit of catalyst layer and contains tar ingredients the tar gas, and the focusing oil content carries out quantitatively estimating the tar resolution ratio thus.Its result, the tar resolution ratio is about 88.5% during through 3 hours after reaction beginning, the hydrogen magnifying power begins slowly to reduce because of sulfur poisoning from initial reaction stage, but reaction beginning after back 4 hours the hydrogen magnifying power stably pass with about 4.5, the catalyst dry gasification that the living beings of having verified the model plant layout contain tar gas is reflected at stably and carries out.
(embodiment 11)
Use the equipment identical with embodiment 8, with 10kg/ hour feed speed to the dried pieces (being classified into 5cm below) of wherein supplying with the castoff identical with build the waste wood sheet and consider the material that (being classified into below the 5cm) mixes with weight ratio at 1: 2 to be worth doing with embodiment 10, utilization remains on 800 ℃ rotary kiln 7 and carries out destructive distillation, contains tar gas (carbonizing gas) thereby produce living beings.With this contain tar gas import to be filled with except form No.18 with embodiment 3 identical the identical preformed catalyst of other and embodiment 8 and temperature be maintained at about 800 ℃ catalyst tower in, it is contacted with catalyst, continued 8 hours and the catalyst decomposes activity that contains tar gas is estimated.In addition, raw material drops into preceding with 5Nm 3/ hour hydrogen carry out reduction in 30 minutes and handle.The inlet gas flow is about 10Nm 3/ hour, the catalyst loading is about 15L.The tar that the living beings of this moment contain in the tar gas is about 14g/Nm 3In addition, by gas chromatography confirm inlet gas form be with coke oven gas approaching with hydrogen, CO, methane, CO 2Composition for main component.In addition, contained about 20% moisture evaporation becomes steam and is contained in this gas in the melange as the dry product of the castoff of raw material and building waste wood.And then, confirm the hydrogen sulfide that contains the 200ppm that has an appointment in this gas.In addition, the method by similarly to Example 5 captures from the entrance and exit of catalyst layer and contains tar ingredients the tar gas, and the focusing oil content carries out quantitatively estimating the tar resolution ratio thus.Its result, the tar resolution ratio is about 87.5% during through 3 hours after reaction beginning, the hydrogen magnifying power begins slowly to reduce because of sulfur poisoning from initial reaction stage, but reaction beginning after back 4 hours the hydrogen magnifying power stably pass with about 4.6, the catalyst dry gasification that the living beings of having verified the model plant layout contain tar gas is reflected at stably and carries out.
(embodiment 12)
After reforming among the embodiment 88 hours, stop to supply with coal as raw material, with nitrogen to purging in the system.Then, be taken into a mouthful suction air near the gas the inlet that is arranged at the rotary kiln 7 that remains on 800 ℃, import about 10 hours through the warmed-up air of rotary kiln to catalyst tower, thus will be deposited on the catalyst surface after the reformation separate out carbon and the oxidation of absorption sulphur is removed, regenerate.Then, in order to discharge that oxygen divides and with nitrogen to after purging in the system, once more with 5Nm 3/ hour hydrogen carry out reduction in 30 minutes and handle.Then, the speed base feed with identical with embodiment 8 makes it contact with catalyst, continued 8 hours and the catalyst decomposes activity that contains tar gas is estimated.Consequently, the tar resolution ratio after the regeneration, hydrogen magnifying power obtain and the preceding identical numerical value of regeneration, have verified the regeneration of fully having carried out catalyst by air burning.In addition, repeat 5 times this contain the catalyst decomposes of tar gas, catalyst regeneration after this, the hydrogen magnifying power obtain with regenerate before same stable result, as can be known can long-time running.
(embodiment 13)
After reforming among the embodiment 98 hours, stop to supply with building waste wood sheet bits as raw material, similarly to Example 12 with nitrogen to purging in the system.Then, be taken into a mouthful suction air from being arranged near the gas of rotary kiln 7 inlets that remains on 800 ℃, import about 10 hours through the warmed-up air of rotary kiln to catalyst tower, thus will be deposited on the catalyst surface after the reformation separate out carbon and the oxidation of absorption sulphur is removed, regenerate.Then, in order to discharge that oxygen divides and with nitrogen to after purging in the system, once more with 5Nm 3/ hour hydrogen carry out reduction in 30 minutes and handle.Then, the speed base feed with identical with embodiment 9 makes it contact with catalyst, continued 8 hours and the catalyst decomposes activity that contains tar gas is estimated.Consequently, the tar resolution ratio after the regeneration, hydrogen magnifying power obtain and the preceding identical numerical value of regeneration, even also verified the regeneration of fully having carried out catalyst by air burning under the situation of building waste wood sheet bits.In addition, repeat 6 these living beings and contain the catalyst decomposes of tar gas, catalyst regeneration after this, the hydrogen magnifying power obtains and the preceding same stable result of regenerating, as can be known can long-time running.
(embodiment 14)
After reforming among the embodiment 10 8 hours, stop to supply with castoff dried pieces as raw material, similarly to Example 12 with nitrogen to purging in the system.Then, be taken into a mouthful suction air from being arranged near the gas of rotary kiln 7 inlets that remains on 800 ℃, import about 10 hours through the warmed-up air of rotary kiln to catalyst tower, thus will be deposited on the catalyst surface after the reformation separate out carbon and the oxidation of absorption sulphur is removed, regenerate.Then, in order to discharge that oxygen divides and with nitrogen to after purging in the system, once more with 5Nm 3/ hour hydrogen carry out reduction in 30 minutes and handle.Then, the speed base feed with identical with embodiment 10 makes it contact with catalyst, continued 8 hours and the catalyst decomposes activity that contains tar gas is estimated.Consequently, the tar resolution ratio after the regeneration, hydrogen magnifying power obtain and the preceding identical numerical value of regeneration, even also verified the regeneration of fully having carried out catalyst by air burning under the situation of castoff dried pieces.In addition, repeat 5 these living beings and contain the catalyst decomposes of tar gas, catalyst regeneration after this, the hydrogen magnifying power obtains and the preceding same stable result of regenerating, as can be known can long-time running.
(embodiment 15)
After reforming among the embodiment 11 8 hours, stop to supply with castoff dried pieces and building waste wood sheet bits melange as raw material, similarly to Example 12 with nitrogen to purging in the system.Then, be taken into a mouthful suction air from being arranged near the gas of rotary kiln 7 inlets that remains on 800 ℃, import about 10 hours through the warmed-up air of rotary kiln to catalyst tower, thus will be deposited on the catalyst surface after the reformation separate out carbon and the oxidation of absorption sulphur is removed, regenerate.Then, in order to discharge that oxygen divides and with nitrogen to after purging in the system, once more with 5Nm 3/ hour hydrogen carry out reduction in 30 minutes and handle.Then, the speed base feed with identical with embodiment 11 makes it contact with catalyst, continued 8 hours and the catalyst decomposes activity that contains tar gas is estimated.Consequently, the tar resolution ratio after the regeneration, hydrogen magnifying power obtain and the preceding identical numerical value of regeneration, even also verified the regeneration of fully having carried out catalyst by air burning under the situation of castoff dried pieces and building waste wood sheet bits melange.In addition, repeat 5 these living beings and contain the catalyst decomposes of tar gas, catalyst regeneration after this, the hydrogen magnifying power obtains and the preceding same stable result of regenerating, as can be known can long-time running.
(comparative example 1)
Under the condition of the No.8 of embodiment 2, use reforming catalyst (SC11NK of ズ one De ケ ミ, one system naphtha of one of industrial catalyst by the experimental technique identical with embodiment 1; Support Ni-20 quality %) (intensity is up to 500N) as the catalyst test of having carried out reforming, the methane selection rate is 2.5% as a result, the CO selection rate is 4.2%, CO 2Selection rate is 5.9%, and the carbon eduction rate is 32.8%, and resolution ratio is 45.4%, and the hydrogen magnifying power is 1.3.
Therefore, industrial catalyst obtains the result and is, to the conversion ratio low (12.6%) of the gas componant of methyl naphthalene, on the other hand, the carbon eduction rate is very high.Because the carbon eduction rate is very high, so catalyst life is short probably.In addition, even regenerate processing after reaction, also need to carry out high temperature or long oxidation processes, therefore anticipation is at this moment owing to the big combustion heat causes the catalyst activity particles sintering, and the performance after the regeneration further reduces.
(comparative example 2)
Use the testing equipment identical, under the condition identical, the industrial catalyst (SC11NK) of use in the comparative example 1 is set in reaction tube and estimates with embodiment 5 with embodiment 5.Consequently, the tar resolution ratio rests on 22% during through 2 hours after reaction beginning, and the hydrogen magnifying power is counted about 1.5 with 5 hourly averages, even distinguished that the tar resolution ratio is also low in the evaluation of industrial catalyst under actual coke oven gas, actual tar.
(comparative example 3)
After preparing the sediment of nickel and magnesium similarly to Example 1, filter, wash, after the drying, in air, carry out under 950 ℃ burning till in 20 hours, obtain nickel and magnesian compound.Then, add silicon dioxide gel and make SiO in the catalyst 2Reach the ratio of 50 quality %, thereby prepared slurry.Then, reach in average grain diameter under the condition of about 50 μ m and carry out spray-drying, the powder that obtains is thus burnt till under 950 ℃ in air.And then, after by the experimental technique identical the solid solution, oxide that obtains being carried out moulding, burnt till, under the condition identical, carry out activity rating with the No.8 of embodiment 2 with embodiment 1.Consequently, about catalyst activity, the resolution ratio of methyl naphthalene terminates in about 15%, and is very low, and the hydrogen magnifying power is 1.0 also, and becoming does not have result amplified fully, distinguished that catalyst activity is low.
(comparative example 4)
After preparing the sediment of nickel and magnesium similarly to Example 1, filter, wash, drying.Then, in air, burn till under 950 ℃, obtain nickel and magnesian compound.Then, the alumina powder of weighing 50wt% mixes both physical properties with mortar.After by the experimental technique identical this mixture being carried out moulding, burns till, under the condition identical, carry out activity rating with the No.8 of embodiment 2 with embodiment 1.Consequently, about catalyst activity, the resolution ratio of methyl naphthalene is about 66.7%, and the hydrogen magnifying power is 1.6, demonstrate moderate catalyst activity, but intensity is low, has distinguished the intensity for being difficult to use in the practicality.
(comparative example 5)
As disclosed in non-patent literature 1 or the patent documentation 8 etc., prepare by aqueous solution making sediment that contains nickel and magnesia and aluminium oxide and the method for making of burning till by utilizing precipitating reagent.Promptly, reached 1: 9 and calculate and accurately take by weighing nickel nitrate, magnesium nitrate and aluminum nitrate according to the mol ratio of nickel and the metallic element of magnesium and embodiment 1 are identical in the mode that aluminium oxide is counted 50wt%, mix with 60 ℃ pure water and prepare mixed solution, to wherein adding the wet chemical that is heated to 60 ℃ similarly to Example 1, stir fully with agitator.Then, continue under 60 ℃ the state to stir the stipulated time and after carrying out slaking, carry out suction filtration remaining on, wash fully with 80 ℃ pure water.Then, this sediment transferred under 120 ℃, carry out drying in the evaporating dish, after pulverizing with mortar, use the compression molding device, obtain the tablet formed body powder compression moulding similarly to Example 1.This formed body is burnt till under 1100 ℃ in air, thereby prepared molded catalyst bodies.Use this molded catalyst bodies under the condition identical, to carry out activity rating with the No.8 of embodiment 2.Consequently, about catalyst activity, the resolution ratio of methyl naphthalene is about 62.6% (wherein, the carbon eduction rate is 19.9%), and the hydrogen magnifying power is 1.6, only demonstrates moderate catalyst activity, has distinguished that the carbon amount of separating out is very many.
In addition, by method similarly to Example 2, reacted catalyst is pulverized, the Ni grain of being obtained by the Ni that utilizes the wide-angle x-ray diffraction to obtain (200) peak is calculated and is 35nm as shown in Figure 4, because Ni can't be from separating out imperceptibly by the compound of this method preparation, so think that the result is that the carbon amount of separating out is many and reforming activity is also low.
Symbol description
1 tedge
2 ammoniacal liquor
3 coke ovens
4 dry mains
5 raw materials buckets
6 weight feed machines
7 external-heating rotary kilns
8 catalyst towers
9 water scrubbers
10 oily bubblers
11 induction fans
12 amplify flare tower

Claims (18)

1. a manufacture method that contains the catalyst for reforming of tar gas is characterized in that, adds precipitating reagent in the mixed solution of nickel compound and magnesium compound, makes nickel and magnesium co-precipitation and generates sediment; In this sediment, add alumina powder and water or add alumina sol and mix and generate mixture; This mixture is carried out drying at least and burns till, thereby make catalyst.
2. the manufacture method that contains the catalyst for reforming of tar gas according to claim 1 is characterized in that, described mixture is carried out drying and burns till or carry out drying, calcining, pulverizing, moulding and burn till, thereby make catalyst.
3. the manufacture method that contains the catalyst for reforming of tar gas according to claim 1, it is characterized in that the catalyst for reforming that contains tar gas of described manufacturing is that 1～50 quality %, content of magnesium are that the content of 5～45 quality %, aluminium oxide is that the mode of 20～80 quality % is made according to nickel content.
4. the manufacture method that contains the catalyst for reforming of tar gas according to claim 3, it is characterized in that the catalyst for reforming that contains tar gas of described manufacturing is that 1～35 quality %, content of magnesium are that the content of 10～25 quality %, aluminium oxide is that the mode of 20～80 quality % is made according to nickel content.
5. a manufacture method that contains the catalyst for reforming of tar gas is characterized in that, adds precipitating reagent in the mixed solution of nickel compound and magnesium compound, makes nickel and magnesium co-precipitation and generates sediment; In this sediment, add alumina powder and water or add alumina sol and mix and generate mixture; With this mixture after the dry and calcining, further mixed oxidization aluminium powder and water or mixed aluminium oxides colloidal sol and generate the 2nd mixture; The 2nd mixture is carried out drying at least and burns till, thereby make catalyst.
6. the manufacture method that contains the catalyst for reforming of tar gas according to claim 5 is characterized in that, described the 2nd mixture is carried out drying and burns till or carry out drying, calcining, pulverizing, moulding and burn till, thereby make catalyst.
7. the manufacture method that contains the catalyst for reforming of tar gas according to claim 5, it is characterized in that the catalyst for reforming that contains tar gas of described manufacturing is that 1～50 quality %, content of magnesium are that the content of 5～45 quality %, aluminium oxide is that the mode of 20～80 quality % is made according to nickel content.
8. the manufacture method that contains the catalyst for reforming of tar gas according to claim 7, it is characterized in that the catalyst for reforming that contains tar gas of described manufacturing is that 1～35 quality %, content of magnesium are that the content of 10～25 quality %, aluminium oxide is that the mode of 20～80 quality % is made according to nickel content.
9. reforming method that contains tar gas, it has used the catalyst for reforming that contains tar gas by each described manufacture method manufacturing in the claim 1～8.
10. the reforming method that contains tar gas according to claim 9, it is characterized in that, described contain the tar gas catalyst for reforming in the presence of or in the presence of the described catalyst after the reduction, make it to contact with the hydrogen, carbon dioxide and the steam that contain in the tar gas that with the carbon raw material thermal decomposition time, produce, thereby with described coke tar reforming and the gasification that contains in the tar gas.
11. the reforming method that contains tar gas according to claim 10, it is characterized in that, the tar gas that contains that produces when making described thermal decomposition contacts any gas at least hydrogen, carbon dioxide, the steam from the outside, thereby contains with described that tar gas is reformed and gasification.
12. the reforming method that contains tar gas according to claim 9 is characterized in that, the described tar gas that contains is the tar gas that contains that contains the above hydrogen sulfide of 20ppm.
13. the reforming method that contains tar gas according to claim 9 is characterized in that, further adds oxygen-containing gas and it is contacted with the described tar gas that contains in gas to described reformation, thereby described part hydrogen or the hydrocarbon that contains in the tar gas burnt.
14. the reforming method that contains tar gas according to claim 9 is characterized in that, the described tar gas that contains is the carbonizing gas that produces when coal is carried out destructive distillation.
15. the reforming method that contains tar gas according to claim 9 is characterized in that, the described tar gas that contains is the coke oven gas of discharging from coke oven.
16. the reforming method that contains tar gas according to claim 9 is characterized in that, described contain tar gas be to wooden be living beings, castoff be in the living beings any one carries out destructive distillation at least the time carbonizing gas that produces.
17. the reforming method that contains tar gas according to claim 9 is characterized in that, the described tar gas that contains is contacted with the described tar gas catalyst for reforming that contains down at 600～1000 ℃.
18. renovation process that contains the catalyst for reforming of tar gas, it is characterized in that, by the described enforcement that contains the reforming method of tar gas of claim 9, described catalyst owing to carbon is separated out, in the sulfur poisoning any one has taken place under the situation of performance degradation at least, make steam or airborne any one contacts with described catalyst at least, thereby with described catalyst regeneration.
CN2009801369557A 2008-09-24 2009-09-15 Method for producing catalyst for reforming tar-containing gas, method for reforming tar and method for regenerating catalyst for reforming tar-containing gas Pending CN102159313A (en)

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